Desulfurization and novel process for same

ABSTRACT

A composition comprising a metal oxide and a promoter, wherein at least a portion of the promoter is present as a reduced valence promoter, and methods of preparing such composition are disclosed. The thus-obtained composition is employed in a desulfurization zone to remove sulfur from a hydrocarbon stream.

FIELD OF THE INVENTION

This invention relates to the removal of sulfur from hydrocarbonstreams. In another aspect, this invention relates to compositionssuitable for use in the desulfurization of fluid streams of crackedgasolines and diesel fuels. A further aspect of this invention relatesto processes for the production of compositions for use in the removalof sulfur bodies from fluid streams of cracked gasolines and dieselfuels.

BACKGROUND OF THE INVENTION

The need for cleaner burning fuels has resulted in a continuingworldwide effort to reduce sulfur levels in hydrocarbon streams such asgasoline and diesel fuels. The reduction of sulfur in such hydrocarbonstreams is considered to be a means for improving air quality because ofthe negative impact the sulfur has on performance of sulfur sensitiveitems such as automotive catalytic converters. The presence of oxides ofsulfur in automotive engine exhaust inhibits and may irreversibly poisonnoble metal catalysts contained in the converter. Emissions from aninefficient or poisoned converter contain levels of non-combusted,non-methane hydrocarbons, oxides of nitrogen, and carbon monoxide. Suchemissions are catalyzed by sunlight to form ground level ozone, morecommonly referred to as smog.

Thermally processed gasolines such as, for example, thermally crackedgasoline, visbreaker gasoline, coker gasoline and catalytically crackedgasoline (hereinafter collectively referred to as “cracked gasoline”)contains, in part, olefins, aromatics, sulfur, and sulfur containingcompounds. Since most gasolines, such as, automobile gasolines, racinggasolines, aviation gasolines, boat gasolines, and the like contain ablend of, at least in part, cracked gasoline, reduction of sulfur incracked gasoline will inherently serve to reduce the sulfur levels inmost gasolines, such as, for example, automobile gasolines, racinggasolines, aviation gasolines, boat gasolines, and the like.

The public discussion about gasoline sulfur has not centered on whetheror not sulfur levels should be reduced. A consensus has emerged thatlower sulfur gasoline reduces automotive emissions and improves airquality. Thus, the rules to date have focused on the required level ofreduction, the geographical areas in need of lower sulfur gasoline, andthe time frame for implementation.

As the concern over the impact of automotive air pollution continues, itis clear that further effort to reduce the sulfur level in automotivefuels will be required. While the current gasoline products containabout 330 parts per million (ppm) sulfur, the US EnvironmentalProtection Agency recently issued regulations requiring the averagesulfur content in gasoline to be less than 30-ppm average with an 80-ppmcap. By 2008, the standards will effectively require every blend ofgasoline sold in the United States to meet the 30-ppm level.

In addition to the need to be able to produce low sulfur contentautomotive fuels, there is also a need for a process, which will have aminimal effect on the olefin content of such fuels so as to maintain theoctane number (both research and motor octane number). Such a processwould be desirable since saturation of olefins greatly affects theoctane number. Such adverse effect on the olefin content is generallydue to the severe conditions normally employed, such as duringhydrodesulfurization, to remove thiophenic compounds (such as, forexample, thiophenes, benzothiophenes, alkyl thiophenes,alkylbenzothiophenes, alkyl dibenzothiophenes and the like) which aresome of the most difficult sulfur containing compounds to remove fromcracked gasoline. In addition, there is a need to avoid a system whereinthe conditions are such that the aromatic content of the crackedgasoline is lost through saturation. Thus, there is a need for aprocess, which achieves desulfurization and maintains the octane number.

In addition to the need for removal of sulfur from cracked gasolines,there is a need for the petroleum industry to reduce the sulfur contentin diesel fuels. In general, it is much harder to remove sulfur fromdiesel as compared to gasoline. In removing sulfur from diesel fuels byhydrodesulfurization, the cetane is improved but there is a large costin hydrogen consumption. Such hydrogen is consumed by bothhydrodesulfurization and aromatic hydrogenation reaction.

Thus, there is a need for a desulfurization process without asignificant consumption of hydrogen so as to provide a more economicalprocess for the treatment of cracked gasolines and diesel fuels.

As a result of the lack of success in providing a successful andeconomically feasible process for the reduction of sulfur levels incracked gasolines and diesel fuels, it is apparent that there is a needfor a better process for the desulfurization of such hydrocarbon streamswhich has minimal effect on octane levels while achieving high levels ofsulfur removal.

Traditionally, compositions used in processes for the removal of sulfurfrom hydrocarbon streams have been agglomerates used in fixed bedapplications. Because of the various process advantages of fluidizedbeds, hydrocarbon streams are sometimes processed in fluidized bedreactors. Fluidized bed reactors have advantages over fixed bedreactors, such as, for example, better heat transfer and better pressuredrop. Fluidized bed reactors generally use reactants that areparticulate. The size of these particulates is generally in the range offrom about 1 micron to about 1000 microns. However, the reactants usedgenerally do not have sufficient attrition resistance for allapplications. Consequently, finding a composition with sufficientattrition resistance that removes sulfur from these hydrocarbon streamsand that can be used in fluidized, transport, moving, or fixed bedreactors and producing that composition in an economical manner isdesirable and would be a significant contribution to the art and to theeconomy.

SUMMARY OF THE INVENTION

It is thus an object of the present invention is to provide novelmethods for the production of compositions, which are usable in thedesulfurization of hydrocarbon streams.

Another object of the present invention is to provide a process for theremoval of sulfur from hydrocarbon streams, which minimizes theconsumption of hydrogen and the saturation of olefins and aromaticscontained in such streams.

A still further object of the present invention is to provide anincreased content of a promoter component in compositions, whichfacilitate the removal of sulfur from diesel fuel.

A still further object of the present invention is to provide adesulfurized cracked gasoline that contains less than about 100 ppm,preferably less than 50 ppm, of sulfur based on the weight of thedesulfurized cracked gasoline, and which contains essentially the sameamount of olefins and aromatics as are in the cracked gasoline fromwhich such desulfurized cracked gasoline was made. Another furtherobject is to provide a desulfurized diesel fuel.

The first embodiment of this invention includes a novel method for theproduction of a composition comprising:

-   -   a) admixing: 1) a liquid, 2) a zinc-containing compound, 3) a        silica-containing material, 4) alumina, and 5) a promoter so as        to form a mixture thereof;    -   b) drying the mixture so as to form a dried mixture;    -   c) calcining the dried mixture so as to form a calcined mixture;    -   d) reducing the calcined mixture with a suitable reducing agent        under suitable conditions to produce a composition having a        reduced valence promoter content therein, and    -   e) recovering the composition.

The second embodiment of this invention includes another novel methodfor the production of a composition comprising:

-   -   a) admixing: 1) a liquid, 2) a metal-containing compound, 3) a        silica-containing material, 4) alumina, and 5) a first promoter        so as to form a mixture thereof;    -   b) drying the mixture so as to form a dried mixture;    -   c) incorporating a second promoter onto or into the dried        mixture to form an incorporated mixture;    -   d) drying the incorporated mixture to form a dried incorporated        mixture;    -   e) calcining the dried incorporated mixture to form a calcined        promoted mixture;    -   f) reducing the calcined promoted mixture with a suitable        reducing agent under suitable conditions to produce a        composition having a reduced valence promoter content therein;        and    -   g) recovering the composition.

The third embodiment of this invention includes a process for theremoval of sulfur from a hydrocarbon stream comprising:

-   -   a) contacting the hydrocarbon stream with a composition from the        first or second embodiments in a desulfurization zone under        conditions such that there is formed a desulfurized hydrocarbon        stream and a sulfurized composition;    -   b) separating the desulfurized hydrocarbon stream from the        sulfurized composition thereby forming a separated desulfurized        hydrocarbon stream and a separated sulfurized composition;    -   c) regenerating at least a portion of the separated sulfurized        composition in a regeneration zone so as to remove at least a        portion of the sulfur contained therein and/or thereon thereby        forming a regenerated composition;    -   d) reducing the regenerated composition in a reduction zone so        as to provide a reduced composition having a reduced valence        promoter content therein which will effect the removal of sulfur        from a hydrocarbon stream when contacted with same; and        thereafter    -   e) returning at least a portion of the reduced composition to        the desulfurization zone.

Other aspects, objectives, and advantages of the present invention willbe apparent from the detailed description of the invention and theappended claims.

DETAILED DESCRIPTION OF THE INVENTION

The term “gasoline” denotes a mixture of hydrocarbons boiling in therange of from about 37.8° C. to about 260° C., or any fraction thereof.Examples of suitable gasoline include, but are not limited to,hydrocarbon streams in refineries such as naphtha, straight run naphtha,coker naphtha, catalytic gasoline, visbreaker naphtha, alkylate,isomerate, reformate, and the like and combinations thereof.

The term “cracked gasoline” denotes a mixture of hydrocarbons boiling inthe range of from about 37.8° C. to about 260° C., or any fractionthereof, that are products from either thermal or catalytic processesthat crack larger hydrocarbon molecules into smaller molecules. Examplesof suitable thermal processes include, but are not limited to, coking,thermal cracking, visbreaking, and the like and combinations thereof.Examples of suitable catalytic cracking processes include, but are notlimited to, fluid catalytic cracking, heavy oil cracking, and the likeand combinations thereof. Thus, examples of suitable cracked gasolineinclude, but are not limited to, coker gasoline, thermally crackedgasoline, visbreaker gasoline, fluid catalytically cracked gasoline,heavy oil cracked gasoline, and the like and combinations thereof. Insome instances, the cracked gasoline may be fractionated and/orhydrotreated prior to desulfurization when used as a hydrocarbon streamin the process of the present invention.

The term “diesel fuel” denotes a mixture of hydrocarbons boiling in therange of from about 148.9° C. to about 398.9° C., or any fractionthereof. Examples of suitable diesel fuels include, but are not limitedto, light cycle oil, kerosene, jet fuel, straight-run diesel,hydrotreated diesel, and the like and combinations thereof.

The term “sulfur” denotes sulfur in any form such as elemental sulfur ora sulfur compound normally present in a hydrocarbon-containing fluidsuch as cracked gasoline or diesel fuel. Examples of sulfur which can bepresent during a process of the present invention usually contained in ahydrocarbon stream, include, but are not limited to, hydrogen sulfide,carbonyl sulfide (COS), carbon disulfide (CS₂), mercaptans (RSH),organic sulfides (R-S-R), organic disulfides (R-S-S-R), thiophenes,substituted thiophenes, organic trisulfides, organic tetrasulfides,benzothiophenes, alkyl thiophenes, alkyl benzothiophenes, alkyldibenzothiophenes, and the like and combinations thereof as well as theheavier molecular weights of same which are normally present in a dieselfuel of the types contemplated for use in a process of the presentinvention, wherein each R can be an alkyl or cycloalkyl or aryl groupcontaining one carbon atom to ten carbon atoms.

The term “fluid” denotes gas, liquid, vapor, and combinations thereof.

The term “gaseous” denotes that state in which thehydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel,is primarily in a gas or vapor phase.

The term “attrition resistance” denotes the attrition resistance of acomposition produced by the inventive method(s). The term “DavisonIndex” (“DI”) refers to a measure of a composition's resistance toparticle size reduction under controlled conditions of turbulent motion.The higher the value of the measured DI, the lower the attritionresistance of the composition.

The term “metal” denotes metal in any form such as elemental metal or ametal-containing compound. In the method of the first embodiment,preferably a zinc-containing compound is used, producing a compositioncontaining a zinc oxide.

The term “metal oxide”, as used herein, denotes any oxide of a metal.

The term “metal oxide” also denotes metal oxide in any form such as ametal oxide or a metal oxide precursor.

The metal oxide will preferably be present in the composition producedby the inventive method in an amount in the range of from about 10 toabout 90 weight percent metal oxide based on the total weight of theinventive composition, more preferably in an amount in the range of fromabout 30 to about 80 weight percent metal oxide, and most preferably inan amount in the range of from about 40 to about 70 weight percent metaloxide.

The term “promoter” denotes any component, which when added to thecomposition of the present invention, helps promote the desulfurizationof hydrocarbon streams. Such promoters can be at least one metal, metaloxide, precursor for the metal oxide, solid solution of more than onemetal, or alloy of more than one metal wherein the metal component isselected from the group consisting of nickel, cobalt, iron, manganese,copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium,gold, platinum, ruthenium, iridium, chromium, palladium, titanium,zirconium, rhodium, rhenium, and combinations of any two or morethereof.

Some examples of promoter metal containing compounds include metalacetates, metal carbonates, metal nitrates, metal sulfates, metalthiocyanates, and the like and combinations thereof. Preferably, themetal of the promoter is nickel.

The inventive composition having a reduced valence promoter content is acomposition that has the ability to react chemically and/or physicallywith sulfur. It is also preferable that the inventive compositionremoves diolefins and other gum forming compounds from cracked gasoline.

During the preparation of a composition of the present invention, thepromoter, selected from the group consisting of metals, metal oxides,and the like, and combinations thereof may initially be in the form of ametal-containing compound and/or a metal oxide precursor. It should beunderstood that when the promoter is initially a metal-containingcompound and/or a metal oxide precursor, a portion of, or all of, suchcompound and/or precursor may be converted to the corresponding metal ormetal oxide of such compound and/or precursor during the inventiveprocess disclosed herein.

Typically, the common oxidation state of the promoter is combined withthe metal oxide portion of the inventive composition produced by theinventive methods. The number of oxygen atoms associated with thepromoter must be reduced to form a reduced valence promoter.Consequently, at least a portion of the promoter present in theinventive composition must be present as a reduced valence promoter.While not wishing to be bound by theory, it is believed that the reducedvalence promoter can chemisorb, cleave, or remove sulfur. Thus, eitherthe number of oxygen atoms associated with the promoter is reduced orthe oxidation state of the promoter is a zero-valent metal. For example,if nickel is the promoter metal, nickel oxide (NiO) can be used and thereduced valence nickel (promoter metal) can be either nickel metal (Ni⁰)or a non-stoichiometric nickel oxide having a formula of NiO_((1-x))wherein 0<x<1. If tungsten is the promoter, tungsten oxide (WO₃) can beused and the reduced valence tungsten (promoter metal) can be eithertungsten oxide (WO₃), tungsten metal (W⁰), or a non-stoichiometrictungsten oxide having a formula of WO_((3-y)) wherein 0<y<3.

Preferably, the promoter is present in an amount, which will effect theremoval of sulfur from the hydrocarbon stream when contacted with thecomposition under desulfurization conditions. Of the total quantity ofthe promoter present in the inventive composition, it is preferred forat least about 10 weight percent of the promoter to be present in theform of a reduced valence promoter, more preferably at least about 40weight percent of the promoter is a reduced valence promoter, and mostpreferably at least 80 weight percent of the promoter is a reducedvalence promoter for best activity in sulfur removal. The reducedvalence promoter will generally be present in the inventive compositionin an amount in the range of from about 1 to about 60 weight percentreduced valence promoter based on the total weight of the inventivecomposition, preferably in an amount in the range of from about 5 toabout 40 weight percent reduced valence promoter, and most preferably inan amount in the range of from 8 to 20 weight percent reduced valencepromoter for best activity in sulfur removal. When the promotercomprises a bimetallic promoter, the bimetallic promoter should comprisea ratio of the two metals forming such bimetallic promoter in the rangeof from about 20:1 to about 1:20.

The silica-containing material used in the preparation of, and presentin the compositions produced by the inventive methods may be either inthe form of silica or in the form of one or more silica-containingmaterials.

Any suitable silica-containing material may be employed in thecomposition such as, for example, diatomite, expanded perlite, colloidalsilica, silica gel, precipitated silica, and the like, and combinationsthereof. In addition, silicon compounds that are convertible to silicasuch as silicic acid, ammonium silicate, and the like, and combinationsthereof can also be employed.

More preferably the silica-containing material is in the form of crushedexpanded perlite. The term “perlite” as used herein is the petrographicterm for a siliceous volcanic rock, which naturally occurs in certainregions throughout the world. The distinguishing feature, which sets itapart from other volcanic minerals, is its ability to expand four totwenty times its original volume when heated to certain temperatures.When heated above 871.1° C., crushed perlite expands due to the presenceof combined water within the crude perlite rock. The combined watervaporizes during the heating process and creates countless tiny bubblesin the heat softened glassy particles. The glass sealed bubbles accountfor its light weight. Expanded perlite can be crushed to produce aporosity enhancing powder with a weight as little as 2.5 lbs per cubicfoot.

The typical elemental analysis of expanded perlite is: silicon 33.8%,aluminum 7%, potassium 3.5%, sodium 3.4%, calcium 0.6%, magnesium 0.2%,iron 0.6%, trace elements 0.2%, oxygen (by difference) 47.5%, and boundwater 3%.

Typical physical properties of expanded polite are: softening point1600-2000° F., fusion point 2300-2450° F., pH 6.6-6.8, and specificgravity 2.2-2.4.

The term “crushed expanded perlite” or “milled expanded perlite” as usedherein denotes that form of expanded perlite which has first beensubjected to milling so as to yield a particle size of about 20 micronsto about 500 microns, and then heated with a flame at a temperature ofabout 871.1° C., and finally subjected to crushing in a hammer mill.While not wishing to be bound to any particular theory, it is believedthat the shape of the crushed expanded perlite impacts the activity ofthe final composition produced by the inventive methods.

The compositions produced by the inventive methods contain analuminum-containing material selected from the group consisting ofalumina, aluminate, and combinations thereof. Alumina can be used toproduce the compositions. The alumina employed in the preparation of thecompositions can be any suitable commercially availablealuminum-containing substance of which at least a portion can beconverted to an aluminate upon calcinations. Examples include, but arenot limited to, aluminum chlorides, aluminum nitrates, colloidal aluminasolutions, hydrated aluminas, peptized aluminas, and, generally, thosealumina compounds produced by the dehydration of alumina hydrates. Thepreferred alumina is hydrated alumina such as, for example, bohemite orpseudobohemite for best activity and sulfur removal. When a compositionis exposed to high temperatures (e.g., during calcinations) at least aportion, preferably a substantial portion of the alumina can beconverted to an aluminate, preferably a zinc aluminate spinel.

The aluminum-containing material will preferably be present in acomposition produced by the inventive methods in an amount in the rangeof from about 1.0 to about 30 weight percent, preferably in an amount inthe range of from about 5 to about 25 weight percent, and mostpreferably, in the range of from 10 to 22 weight percent, based on thetotal weight of the composition.

The silica-containing material will preferably be present in acomposition produced by the inventive methods in an amount in the rangeof from about 10 to about 40 weight percent silica-containing materialbased on the total weight of the composition, more preferably in anamount in the range of from about 12 to about 35 weight percent, andmost preferably in the range of from 15 to 30 weight percent.

The composition can be a particulate in the form of one of granules,extrudates, tablets, spheres, pellets, or microspheres. Preferably, theparticulate is a fluidizable microsphere.

In accordance with the first embodiment of the present invention, acomposition can be produced by the following inventive method.

In the inventive production method, the composition can generally beprepared by admixing a liquid, a zinc-containing compound, asilica-containing material, alumina, and a promoter in appropriateproportions by any suitable method or manner which provides for theintimate mixing of such components to thereby provide a substantiallyhomogenous mixture thereof comprising a liquid, a zinc-containingcompound, a silica-containing material, alumina, and a promoter. Theterm “admixing,” as used herein, denotes mixing components in any orderand/or any combination or sub-combination. Any suitable means foradmixing the components of the composition can be used to achieve thedesired dispersion of such components. Examples of suitable admixinginclude, but are not limited to, mixing tumblers, stationary shelves ortroughs, Eurostar mixers, which are of the batch or continuous type,impact mixers, and the like. It is presently preferred to use a Eurostarmixer in the admixing of the components of the inventive composition.

The liquid can be any solvent capable of dispersing a metal-containingcompound, a silica-containing material, alumina, and a promoter, and,preferably, the liquid can be selected from the group consisting ofwater, ethanol, acetone and combinations of any two or more thereof.Most preferably, the liquid is water.

The metal-containing compound (preferably a zinc-containing compound)used in the preparation of a composition in the first embodiment of thepresent inventive method can either be in the form of a metal oxide orin the form of one or more metal compounds that are convertible to ametal oxide under the conditions of preparation described herein.Examples of suitable metal compounds include, but are not limited to, ametal sulfide, a metal sulfate, a metal hydroxide, a metal nitrate, andthe like and combinations thereof. Preferably, the metal-containingcompound is in the form of a powdered metal oxide.

The above-listed components of the composition are mixed to provide amixture which can be in the form selected from the group consisting of awet mix, dough, paste, slurry and the like. Preferably, the mixture isin the form of a slurry. Such mixture can then be shaped to form aparticulate selected from the group consisting of a granule, anextrudate, a tablet, a sphere, a pellet, or a microsphere.

When the particulation is achieved, preferably by spray drying, adispersant component can optionally be utilized and can be any suitablecompound that helps to promote the spray drying ability of the mix,which is preferably in the form of a slurry. In particular, thesecomponents are useful in preventing deposition, precipitation, settling,agglomerating, adhering, and caking of solid particles in a fluidmedium. Suitable dispersants include, but are not limited to, condensedphosphates, sulfonated polymers, and combinations thereof. The term“condensed phosphates” refers to any dehydrated phosphate containingmore than one phosphorus atom and having a phosphorus-oxygen-phosphorusbond. Specific examples of suitable dispersants include sodiumpyrophosphate, sodium metaphosphate, sulfonated styrene maleic anhydridepolymer, and combinations thereof. The amount of dispersant componentused is generally in the range of from about 0.01 weight percent basedon the total weight of the components to about 10 weight percent.Preferably, the amount of the dispersant component used is generally inthe range of from about 0.1 weight percent to about 8 weight percent.

In preparing the preferred spray dried composition, an acid componentcan be used. In general, the acid in the acid component can be anorganic acid or a mineral acid such as nitric acid. If the acidcomponent is an organic acid, it is preferred to be a carboxylic acid.If the acid component is a mineral acid, it is preferred to be a nitricacid or a phosphoric acid. Mixtures of these acids can also be used.Generally, the acid is used with water to form a dilute aqueous acidsolution. The amount of acid in the acid component is generally in therange of from about 0.01 volume percent based on the total volume of theacid component to about 20 volume percent.

Generally, the spray-dried material has a mean particle size in therange of from about 10 micrometers to about 1000 micrometers, preferablyin the range of from about 20 micrometers to from about 150 micrometers.

The term “mean particle size” refers to the size of the particulatematerial as determined by using a RO-TAP® Testing Sieve Shaker,manufactured by W. S. Tyler Inc., of Mentor, Ohio, or other comparablesieves. The material to be measured is placed in the top of a nest ofstandard 8-inch diameter stainless steel framed sieves with a pan on thebottom. The material undergoes sifting for a period of about 10 minutes;thereafter, the material retained on each sieve is weighed. The percentretained on each sieve is calculated by dividing the weight of thematerial retained on a particular sieve by the weight of the originalsample. This information is used to compute the mean particle size.

The mixture is then dried to form a dried mixture. The dryingconditions, as referred to herein, can include a temperature in therange of from about 65.5° C. to about 550° C., preferably in the rangeof from about 87.8° C. to about 210° C. and, most preferably, in therange of from 93.3° C. to 176.7° C. Such drying conditions can alsoinclude a time period generally in the range of from about 0.5 hour toabout 60 hours, preferably in the range of from about 1 hour to about 40hours, and most preferably, in the range of from 1.5 hours to 20 hours.Such drying conditions can also include a pressure generally in therange of from about atmospheric (i.e., about 14.7 pounds per square inchabsolute) to about 150 pounds per square inch absolute (psia),preferably in the range of from about atmospheric to about 100 psia and,most preferably about atmospheric, so long as the desired temperaturecan be maintained. Any drying method(s) known to one skilled in the artsuch as, for example, air drying, heat drying, and the like andcombinations thereof can be used. Preferably, heat drying is used.

The dried mixture is then calcined to form a calcined mixture.Preferably, the dried mixture is calcined in an oxidizing atmospheresuch as in the presence of oxygen or air. The calcining conditions, asreferred to herein, can include a temperature in the range of from about204.4° C. to about 815.5° C., preferably in the range of from about426.7° C. to about 815.5° C. and, more preferably, in the range of from482.2° C. to 760° C. Such calcining conditions can also include apressure, generally in the range of from about 7 psia to about 750 psia,preferably in the range of from about 7 psia to about 450 psia and, mostpreferably, in the range of from 7 psia to 150 psia, and a time periodin the range of from about 1 hour to about 60 hours, preferably for atime period in the range of from about 1 hour to about 20 hours and,most preferably, for a time period in the range of from 1 hour to 15hours. In the process of this invention, the calcination can convert atleast a portion of the alumina to an aluminate.

The calcined mixture is thereafter subjected to reduction with asuitable reducing agent, preferably hydrogen, so as to produce acomposition having a substantially reduced valence promoter contenttherein, preferably a substantially zero-valent promoter contenttherein, with such zero-valent promoter being present in an amountsufficient to permit the removal of sulfur from a hydrocarbon streamsuch as cracked gasoline or diesel fuel, according to the processdisclosed herein.

The reduction conditions can include a temperature in the range of fromabout 37.8° C. to about 815.5° C., a pressure in the range of from about15 psia to about 1500 psia and for a time sufficient to permit theformation of a reduced valence promoter.

The composition is then recovered.

In accordance with the second embodiment of the present invention, thecomposition can also be produced by the following inventive method;

-   -   a) admixing: 1) a liquid, 2) a metal-containing compound, 3) a        silica-containing material, 4) alumina, and 5) a first promoter        so as to form a mixture thereof;    -   b) drying the mixture to form a dried mixture;    -   c) incorporating a second promoter onto or into the dried        mixture to form an incorporated mixture;    -   d) drying the incorporated mixture to form a dried incorporated        mixture;    -   e) calcining the dried incorporated mixture to form a calcined        promoted mixture;    -   f) reducing the calcined promoted mixture with a suitable        reducing agent under suitable conditions to produce a        composition having a reduced valence promoter content therein;        and    -   g) recovering the composition.

In the production of a composition of the present invention, thecomposition can generally be prepared by admixing a liquid, ametal-containing compound, a silica-containing material, alumina, and afirst promoter in appropriate proportions by any suitable methods ormanner which provides for the intimate mixing of such components tothereby provide a substantially homogenous mixture comprising a liquid(as described above), a metal-containing compound, a silica-containingmaterial, alumina, and a promoter. Any suitable means for admixing thesecomponents, as described above, can be used to achieve the desireddispersant of such components.

The metal in the metal-containing compound is selected from the groupconsisting of zinc, manganese, silver, copper, cadmium, tin, lanthanum,scandium, cerium, tungsten, molybdenum, iron, niobium, tantalum,gallium, indium, and combinations of any two or more thereof.Preferably, the metal is zinc.

The metal-containing compound used in the preparation of a compositionof the present inventive method can either be in the form of a metaloxide or in the form of one or more metal compounds that are convertibleto a metal oxide under the conditions of preparation described herein.Examples of suitable metal-containing compounds include, but are notlimited to, a metal sulfide, metal sulfate, metal hydroxide, metalcarbonate, metal acetate, metal nitrate, and the like and combinationsthereof. Preferably, the metal-containing compound is in the form of apowdered metal oxide.

The components are mixed to provide a mixture which can be in the formselected from the group consisting of a wet mix, dough, paste, slurry,and the like. Preferably, the mixture is in the form of a slurry. Suchmixture can then optionally be shaped by densifying, extruding, or spraydrying to form a particulate selected from the group consisting of agranule, an extrudate, a tablet, a sphere, a pellet, or a microsphere,as described above.

The mixture is then dried to form a dried mixture, according to thedrying conditions described above.

The dried mixture comprising a metal-containing compound, asilica-containing material, and alumina (or an aluminate), is thenincorporated with a second promoter. Optionally, the dried mixture canbe calcined before the incorporation of the second promoter, accordingto the calcining conditions described above.

The terms “first promoter” and “second promoter” distinguish betweenpromoter components that are added to the mixture at different times.Both components can be comprised of the same element (i.e., nickel) oreach can be comprised of different elements (i.e., the first promotercan comprise nickel and the second promoter can comprise cobalt).Together, the first promoter and the second promoter comprise thepromoter component present in the recovered composition of the secondembodiment.

The second promoter can be incorporated into or onto the dried mixtureby any suitable means or method known in the art for incorporating apromoter into or onto a substrate material.

A preferred method of incorporating is to impregnate using anyconventional wetness impregnation technique (i.e. essentially completelyor partially filling the pores of a substrate material with a solutionof the incorporating elements) for impregnating a substrate. Thispreferred method uses an impregnating solution comprising the desirableconcentration of a promoter to ultimately provide an incorporatedmixture that can then be subjected to drying and calcining (which canconvert at least a portion of the alumina to an aluminate) followed byreduction with a reducing agent such as hydrogen.

A preferred impregnating solution comprises a solution formed bydissolving a metal containing compound, preferably such metal containingcompound is in the form of a metal salt such as a metal chloride, ametal nitrate, a metal sulfate, and the like and combinations thereof,in a solvent such as water, alcohols, esters, ethers, ketones, andcombinations thereof. Preferably, the weight ratio of metal promoter tothe solvent of such solution can be in the range of from about 1:1 toabout 4:1 but, more preferably it is in the range of from 1.5:1 to 3:1.It is preferred for the particulates to be impregnated with a nickelcomponent by use of a solution containing nickel nitrate hexahydratedissolved in water.

Following the incorporating of the dried mixture, preferably byimpregnation, with a second promoter, the resulting incorporated mixtureis then subjected to drying under drying conditions, as described above,to form a dried incorporated mixture, and calcined under calciningconditions, as described above, to form a calcined incorporated mixture.The calcined incorporated mixture can then be subjected to reductionwith a reducing agent, as described above, to thereby provide thecomposition. The composition can then be recovered.

The third embodiment of this invention includes a novel process for theremoval of sulfur from a hydrocarbon stream. This process comprises:

-   -   a) contacting the hydrocarbon stream with a composition of the        first or second embodiments of the present invention in a        desulfurization zone under conditions such that there is formed        a desulfurized hydrocarbon stream and a sulfurized composition;    -   b) separating the desulfurized hydrocarbon stream from the        sulfurized composition thereby forming a separated desulfurized        hydrocarbon stream and a separated sulfurized composition;    -   c) regenerating at least a portion of the separated sulfurized        composition in a regeneration zone so as to remove at least a        portion of the sulfur contained therein and/or thereon thereby        forming a regenerated composition;    -   d) reducing the regenerated composition in a reduction zone so        as to provide a reduced composition having a reduced valence        promoter content therein which will effect the removal of sulfur        from a hydrocarbon stream when contacted with same; and        thereafter    -   e) returning at least a portion of the reduced composition to        the desulfurization zone.

The contacting, in step a), of the hydrocarbon stream with thecomposition prepared by the methods of the first or second embodimentsin the desulfurization zone can be by any method known to those skilledin the art.

The desulfurization zone can be any zone wherein desulfurization of ahydrocarbon stream can take place. Examples of suitable zones are fixedbed reactors, moving bed reactors, fluidized bed reactors, transportreactors, and the like. Presently a fluidized bed reactor or a fixed bedreactor is preferred.

The desulfurization zone of step a) includes the following conditions:total pressure, temperature, weight hourly space velocity, and hydrogenflow. These conditions are such that the inventive composition candesulfurize the hydrocarbon stream to produce a desulfurized hydrocarbonstream and a sulfurized composition.

The total pressure can be in the range of from about 15 pounds persquare inch absolute (psia) to about 1500 psia. However, it is presentlypreferred that the total pressure be in a range of from about 50 psia toabout 500 psia.

In general, the temperature should be sufficient to keep the hydrocarbonstream in essentially a vapor or gas phase. While such temperatures canbe in the range of from about 37.8° C. to about 537.8° C., it ispresently preferred that the temperature be in the range of from about204.4° C. to about 426.7° C. when treating a cracked-gasoline, and inthe range of from about 260° C. to about 482.2° C. when treating adiesel fuel.

Weight hourly space velocity (“WHSV”) is defined as the numerical ratioof the rate at which a hydrocarbon stream is charged to thedesulfurization zone in pounds per hour at standard conditions oftemperature and pressure (STP) divided by the pounds of compositioncontained in the desulfurization zone to which the hydrocarbon stream ischarged. In the practice of the present invention, such WHSV should bein the range of from about 0.5 hr.⁻¹ to about 50 hrs.⁻¹, preferably inthe range of from about 1 hr.⁻¹ to about 50 hrs.⁻¹.

Any suitable hydrocarbon stream, which comprises, consists of, orconsists essentially of sulfur containing hydrocarbons can be used asthe feed to be contacted with the inventive composition. The hydrocarbonstream preferably comprises, consists of, or consists essentially of afuel selected from the group consisting of a cracked gasoline, dieselfuel, and combinations thereof.

The amount of sulfur in the hydrocarbon stream can be in the range offrom about less than 10-ppm sulfur by weight of the hydrocarbon streamto about 50,000 ppm. When the hydrocarbon stream is cracked gasoline,the amount of sulfur can be in the range of from about less than 10 ppmsulfur by weight of the cracked gasoline to about 10,000 ppm sulfur byweight of the cracked gasoline. When the hydrocarbon stream is dieselfuel, the amount of sulfur can be in the range of from about less than10 ppm sulfur by weight of the diesel fuel to about 50,000 ppm sulfur byweight of the diesel fuel.

As used herein, the terms “sulfur” or “ppmw sulfur” denotes the amountof atomic sulfur (about 32 atomic mass units) contained in thesulfur-containing hydrocarbons of the hydrocarbon stream, based on thetotal weight of the hydrocarbon stream, not the atomic mass, or weight,of a sulfur compound, such as an organo-sulfur compound.

The cracked gasoline or diesel fuel, suitable as a feed in a process ofthe present invention, is a composition that contains, in part, olefins,aromatics, sulfur, paraffins and naphthenes.

The amount of olefins in cracked gasoline is generally in the range offrom about 10 to about 35 weight percent olefins based on the totalweight of the cracked gasoline. For diesel fuel there is essentially noolefin content.

The amount of aromatics in cracked gasoline is generally in the range offrom about 20 to about 40 weight percent aromatics based on the totalweight of the cracked gasoline. The amount of aromatics in diesel fuelis generally in the range of from about 10 to about 90 weight percentaromatics based on the total weight of the diesel fuel.

In carrying out the desulfurization step of a process of the presentinvention, it is preferred that the hydrocarbon stream be in a gas orvapor phase. However, in the practice of the present invention, it isnot essential that such hydrocarbon stream be totally in a gas or vaporphase.

In carrying out the desulfurizing step, it is presently preferred thatan agent be employed which interferes with any possible chemical orphysical reacting of the olefinic or aromatic compounds in thehydrocarbon stream which is being treated with the inventivecomposition. Preferably such agent is hydrogen.

Hydrogen flow in the desulfurization zone is generally such that themole ratio of hydrogen to the hydrocarbon stream is the range of fromabout 0.1 to about 10, preferably in the range of from about 0.2 toabout 3.

If desired, during the desulfurization of the cracked gasoline or dieselfuel, diluents such as methane, carbon dioxide, flue gas, nitrogen, andthe like and combinations thereof can be used. Thus, it is not essentialto the practice of the present invention that a high purity hydrogen beemployed in achieving the desired desulfurization of the hydrocarbonstream such as, but not limited to, cracked gasoline or diesel fuel.

It is presently preferred when utilizing a fluidized bed reactor systemthat a composition be used having a particle size in the range of fromabout 10 micrometers to about 1000 micrometers. Preferably, suchcomposition should have a particle size in the range of from about 20micrometers to about 500 micrometers, and, more preferably, in the rangeof from 30 micrometers to 400 micrometers. When a fixed bed reactorsystem is employed for the practice of a desulfurization process of thepresent invention, the composition should generally have a particle sizein the range of about {fraction (1/32)} inch to about {fraction (1/2)}inch diameter, preferably in the range of from about {fraction (1/32)}inch to about {fraction (1/4)} inch diameter.

It is further presently preferred to use a composition having a surfacearea in the range of about 1 square meter per gram (m²/g) to about 1000square meters per gram of composition, preferably in the range of fromabout 1 m²/g to about 800 m²/g.

The desulfurized hydrocarbon stream can be separated from the sulfurizedcomposition by any appropriate separation method known in the artthereby forming a separated desulfurized hydrocarbon stream and aseparated sulfurized composition.

Examples of such means are cyclonic devices, settling chambers,impingement devices for separating solids and gases, and the like andcombinations thereof. Separation can include, but is not limited to,allowing the hydrocarbon stream to flow out of the desulfurization zone.The desulfurized gaseous cracked gasoline or desulfurized gaseous dieselfuel, can then be recovered and preferably liquefied. Liquification ofsuch desulfurized hydrocarbon streams can be accomplished by any mannerknown in the art.

The amount of sulfur in the desulfurized hydrocarbon stream, followingtreatment in accordance with a desulfurization process of the presentinvention, is less than about 500 ppm sulfur by weight of hydrocarbonstream, preferably less than about 150 ppm sulfur by weight ofhydrocarbon stream, and more preferably less than about 50 ppm sulfur byweight of hydrocarbon stream.

In carrying out the process of the present invention, if desired, astripper unit can be inserted before and/or after the regeneration ofthe sulfurized composition. Such stripper will serve to remove aportion, preferably all, of any hydrocarbon from the sulfurizedcomposition. Such stripper can also serve to remove oxygen and sulfurdioxide from the system prior to the introduction of the regeneratedcomposition into the reduction zone. The stripping comprises a set ofconditions that include total pressure, temperature, and a strippingagent partial pressure.

Preferably, the total pressure in the stripper when employed is in therange of from about 25 psia to about 500 psia.

Temperature for such stripping can be in the range of from about 37.8°C. to about 537.8° C.

The stripping agent is a composition that helps to remove hydrocarbonfrom the sulfurized composition. Preferably, the stripping agent isnitrogen. The sulfurized composition can have sulfur contained therein(for example, within the pores of the composition) or thereon (forexample, located on the surface of the composition).

The regeneration zone employs a set of conditions that includes totalpressure and sulfur removing agent partial pressure. The total pressureis generally in the range of from about 25 psia to about 50 psia.

The sulfur removing agent partial pressure is generally in the range offrom about 1% to about 25% of the total pressure.

The sulfur-removing agent is a composition that helps to generategaseous sulfur containing compounds and oxygen containing compounds suchas sulfur dioxide, as well as to burn off any remaining hydrocarbondeposits that might be present. The preferred sulfur removing agentsuitable for use in the regeneration zone is selected from oxygencontaining gases such as, but not limited to, air.

The temperature in the regeneration zone is generally in the range offrom about 37.8° C. to about 815.5° C., preferably in the range of fromabout 426.7° C. to about 648.9° C.

The regeneration zone can be any vessel wherein the desulfurizing orregeneration of the sulfurized composition can take place.

The regenerated composition is then reduced in a reduction zone with areducing agent including, but not limited to, hydrogen, so that at leasta portion of the promoter content of the composition is reduced toproduce a reduced composition having a reduced valence promoter contentto permit the removal of sulfur from the hydrocarbon stream according tothe inventive process disclosed herein.

In general, when practicing the present invention, reduction of thedesulfurized composition is carried out at a temperature in the range offrom about 37.8° C. to about 815.5° C. and at a pressure in the range offrom about 15 psia to about 1500 psia. Such reduction is carried out fora time sufficient to achieve the desired level of promoter reduction ofthe promoter, which is preferably contained in the skin of thecomposition. Such reduction can generally be achieved in a time periodin the range of from about 0.01 hour to about 20 hours.

Following the reduction of the regenerated composition, at least aportion of the resulting reduced composition can be returned to thedesulfurization zone.

In carrying out the process of the present invention, the steps ofdesulfurization, regeneration, reduction, and optionally strippingbefore and/or after such regeneration can be accomplished in the singlezone or vessel or in multiple zones or vessels.

When carrying out the process of the present invention in a fixed bedreactor system, the steps of desulfurization, regeneration, reduction,and optionally stripping before and/or after such regeneration areaccomplished in a single zone or vessel.

The desulfurized cracked gasoline can be used in the formulation ofgasoline blends to provide gasoline products suitable for commercialconsumption and can also be used where a cracked gasoline containing lowlevels of sulfur is desired.

The desulfurized diesel fuel can be used in the formulation of dieselfuel blends to provide diesel fuel products.

EXAMPLE I Inventive

A zinc oxide/alumina/perlite composition promoted with nickel wasprepared. A 56-gram quantity of Vista Dispal alumina was added to 118.43grams of deionized water and was mixed for 20 minutes. Then, a 43.6-gramquantity of a base (prepared by treating perlite with nitric acid, andthen adding alumina, zinc oxide and kaolin clay) was added to themixture of water and alumina over a 5-minute period and was mixed forfive additional minutes. This mixture will be referred to hereinafter asMixture #1.

Meanwhile, a 0.03-gram quantity of nitric acid was added to 473.73 gramsof deionized water and was mixed for five minutes. Then, over afive-minute period, a 55.6-gram quantity of perlite (Silbrico Sil-Kleer#27-M) was added to the nitric acid solution and was mixed for 20minutes. Then, over a 5-minute period, a 198-gram quantity of nickelnitrate was added to the perlite solution and was mixed for 15 minutes.This mixture will be referred to hereinafter as Mixture #2.

Mixture #2 was then poured into Mixture #1 and was then mixed for 10minutes. Then, a 204.8-gram quantity of zinc oxide was added to themixture over a five minute period and was then mixed for an additional15 minutes. The zinc oxide mixture was spray dried, and then dried in anoven.

A 100-gram quantity of the zinc oxide mixture was impregnated via anultra-sonic nozzle with a combination of 87.5 grams of nickel nitratehexahydrate plus 13.75 grams of deionized water. The impregnated mixturewas dried at 150° C. for 1 hour and calcined at 635° C. for 1 hour. TheDavison Index (DI) value for this composition was 10.3.

EXAMPLE II

The composition as prepared in Example I was tested for itsdesulfurization activity as follows. 10 grams of the material asprepared was placed in a ½ inch diameter quartz tube having a length ofabout 12 inches and having a glass frit positioned above the lowerone-third so as to provide an inert support for the bed of thecomposition.

During each reaction cycle, the reactor was maintained at a temperatureof 398.9° C. and a pressure of 15 pounds per square inch absolute(psia). Hydrogen flow was at 130 standard cubic centimeters per minute(sccm) diluted with 130 sccm of nitrogen. A model diesel feed was pumpedupwardly through the reactor at a rate of 13.4 ml per hour. Suchconditions are hereinafter referred to as “reaction conditions.”

The diesel feed had a sulfur content of 135 parts per million (ppm)sulfur. The sulfur was in the form of 4,6-dimethyl dibenzothiophene.This compound is the most difficult sulfur-containing compound to removedue to steric hindrance.

Before Cycle 1 was initiated, the composition was reduced with hydrogenflowing at a rate of 300 sccm at a temperature of 398.9° C. for a periodof one hour. Such conditions are hereinafter referred to as “reducingconditions.” Each reaction cycle consisted of four hours with theproduct sulfur (ppm) for each cycle measured after one, two, three, andfour hours of exposure to the feed.

After completion of the reaction cycle, the composition was flushed with180-sccm nitrogen at 398.9° C. for fifteen minutes. The temperature wasthen raised to 537.8° C. where the composition was regenerated under120-sccm air and 180-sccm nitrogen for two hours. The temperature wasthen decreased to 398.9° C. and the sample purged with nitrogen for 15minutes. Such conditions are hereinafter referred to as “regenerationconditions.” Cycle 2 began, like Cycle 1 under reducing conditions;i.e., with treatment at 398.9° C. of the composition in hydrogen at aflow rate 300 sccm for one hour.

The composition of Example I was tested over two reaction cycles withregeneration occurring after Cycle 1. The results in Table I wereobtained where the values given are the parts per million by weight ofsulfur in the product after the first hour, second hour, third hour, andfourth hour of treatment, respectively. TABLE I Feed: 135 ppm SulfurTime Cycle 1 (ppm S) Cycle 2 (ppm S) First Hour 65 47 Second Hour 82 76Third Hour 86 90 Fourth Hour 91 98

EXAMPLE III Control

A 70-gram quantity of a base (prepared by treating perlite with nitricacid, and then adding alumina, zinc oxide, and kaolin clay) wasimpregnated with nickel in two steps using the conventional wetimpregnation method. Each impregnation was with 74.3 grams of nickelnitrate hexahydrate in 7 grams of deionized water. After the firstimpregnation, the composition was dried at a temperature of 150° C. for1 hour. After the second impregnation the composition was dried at 150°C. for 1 hour and calcined at 635° C. for 1 hour. The DI value for thiscomposition was 12.2.

EXAMPLE IV

10 grams of the composition as prepared in Example III were tested fordesulfurization activity as described in Example II. The composition wastested over two reaction cycle with the results in Table II given inparts per million by weight of sulfur in the product after the firsthour, second hour, third hour, and fourth hour of treatment,respectively. TABLE II Feed - 135 ppm Sulfur Time Cycle 1 (ppm S) Cycle2 (ppm S) First Hour 80  72 Second Hour 90  95 Third Hour 91 101 FourthHour 97 106

EXAMPLE V Control

An 85-gram quantity of a base (as described in Examples I and III) wasimpregnated with nickel in one step using the conventional wetimpregnation method. The impregnation was with 74.3 grams of nickelnitrate hexahydrate in 7 grams deionized water. The composition wasdried at 150° C. for 1 hour and calcined at 635° C. for 1 hour. The DIvalue for this composition was 14.7.

EXAMPLE VI

10 grams of the composition as prepared in Example V were tested fordesulfurization activity as described in Example II. The composition wastested over two reaction cycles with the results in Table III given inparts per million by weight of sulfur in the product after the firsthour, second hour, third hour, and fourth hour of treatment,respectively. TABLE III Feed - 135 ppm Sulfur Time Cycle 1 (ppm S) Cycle2 (ppm S) First Hour 67  63 Second Hour 76  94 Third Hour 81 105 FourthHour 89 108

Based upon the results, the composition prepared by the inventive methodin Example I removes sulfur just as well, if not better, than thecompositions prepared in Examples III and V.

EXAMPLE VII

A zinc oxide/alumina/perlite composition promoted with nickel wasprepared. A 685-gram quantity of distilled water was mixed with 1007.5grams of nickel nitrate hexahydrate. A 146-gram quantity of CondeaDisperal alumina was then added to the mixture. Meanwhile, 150 grams ofperlite (Silbrico Sil-Kleer #27-M) was mixed with 575 grams of zincoxide. This mixture was then added to the alumina mixture. Thecomposition was then dried and calcined as disclosed in the previousexamples.

While this invention has been described in detail for the purpose ofillustration, it should not be construed as limited thereby but intendedto cover all changes and modifications within the spirit and scopethereof.

1. A method for the production of a composition comprising: (a)admixing: 1) a liquid, 2) a zinc-containing compound, 3) asilica-containing material, 4) alumina, and 5) a promoter so as to forma mixture thereof; (b) drying said mixture so as to form a driedmixture; (c) calcining said dried mixture so as to form a calcinedmixture; (d) reducing said calcined mixture with a suitable reducingagent under suitable conditions to produce a composition having areduced valence promoter content therein, and (e) recovering saidcomposition.
 2. A method in accordance with claim 1 wherein saidcalcined mixture is reduced in step (d) such that said composition willeffect the removal of sulfur from a stream of hydrocarbons when suchstream is contacted with same under desulfurization conditions.
 3. Amethod in accordance with claim 1 wherein said promoter comprises ametal selected from the group consisting of nickel, cobalt, iron,manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony,vanadium, gold, platinum, ruthenium, iridium, chromium, palladium,titanium, zirconium, rhodium, rhenium, and combinations of any two ormore thereof.
 4. A method in accordance with claim 3 wherein saidpromoter comprises nickel.
 5. A method in accordance with claim 1wherein said silica-containing material is in the form of crushedexpanded perlite.
 6. A method in accordance with claim 1 wherein saidmixture from step (a) is in the form of one of a wet mix, dough, paste,or slurry.
 7. A method in accordance with claim 6 wherein said mixturefrom step (a) is in the form of a slurry.
 8. A method in accordance withclaim 1 wherein said mixture from step (a) is particulated prior to saiddrying in step (b).
 9. A method in accordance with claim 1 wherein saidmixture from step (a) is particulated in the form of one of granules,extrudates, tablets, spheres, pellets, or microspheres prior to saiddrying in step (b).
 10. A method in accordance with claim 1 wherein saidmixture from step (a) is particulated by spray drying in step (b) so asto form said dried mixture.
 11. A method in accordance with claim 1wherein said mixture is dried in step (b) at a temperature in the rangeof from about 65.5° C. to about 550° C.
 12. A method in accordance withclaim 1 wherein said dried mixture is calcined in step (c) at atemperature in the range of from about 204.4° C. to about 815.5° C. 13.A method in accordance with claim 1 wherein said calcined mixture isreduced in step (d) at a temperature in the range of from about 37.8° C.to about 815.5° C. and at a pressure in the range of from about 15 toabout 1500 psia and for a time sufficient to permit the formation of areduced valence promoter.
 14. A method in accordance with claim 1wherein during said calcining of step (c) at least a portion of saidalumina is converted to an aluminate.
 15. A composition produced by theprocess of claim
 1. 16. A method for the production of a compositioncomprising: (a) admixing: 1) a liquid, 2) a metal-containing compound,3) a silica-containing material, 4) alumina, and 5) a first promoter soas to form a mixture thereof; (b) drying said mixture so as to form adried mixture; (c) incorporating a second promoter onto or into saiddried mixture to form an incorporated mixture; (d) drying saidincorporated mixture so as to form a dried incorporated mixture; (e)calcining said dried incorporated mixture so as to form a calcinedincorporated mixture; (f) reducing said calcined incorporated mixturewith a suitable reducing agent under suitable conditions to produce acomposition having a reduced valence promoter content therein; and (g)recovering said composition.
 17. A method in accordance with claim 16wherein said first promoter comprises a metal selected from the groupconsisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum,tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium,iridium, chromium, palladium, titanium, zirconium, rhodium, rhenium, andcombinations of any two or more thereof.
 18. A method in accordance withclaim 16 wherein said first promoter comprises nickel.
 19. A method inaccordance with claim 16 wherein said calcined incorporated mixture isreduced in step (f) such that said composition of step (g) will effectthe removal of sulfur from a stream of hydrocarbons when such stream iscontacted with same under desulfurization conditions.
 20. A method inaccordance with claim 16 wherein said metal-containing compoundcomprises a metal selected from the group consisting of zinc, manganese,silver, copper, cadmium, tin, lanthanum, scandium, cerium, tungsten,molybdenum, iron, niobium, tantalum, gallium, indium, and combinationsof any two or more thereof.
 21. A method in accordance with claim 20wherein said metal-containing compound comprises zinc.
 22. A method inaccordance with claim 16 wherein said second promoter is comprised of atleast one metal selected from the group consisting of nickel, cobalt,iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin,antimony, vanadium, gold, platinum, ruthenium, iridium, chromium,palladium, titanium, zirconium, rhodium, rhenium, and combinations ofany two or more thereof.
 23. A method in accordance with claim 22wherein said second promoter comprises nickel.
 24. A method inaccordance with claim 16 wherein said silica-containing material ispresent in the form of crushed expanded perlite.
 25. A method inaccordance with claim 16 wherein said mixture from step (a) is in theform of one of a wet mix, dough, paste, or slurry.
 26. A method inaccordance with claim 25 wherein said mixture from step (a) is in theform of a slurry.
 27. A method in accordance with claim 16 wherein saidmixture from step (a) is particulated prior to drying in step (b).
 28. Amethod in accordance with claim 16 wherein said mixture from step (a) isparticulated in the form of one of granules, extrudates, tablets,spheres, pellets, or microspheres.
 29. A method in accordance with claim16 wherein said mixture from step (a) is particulated by spray drying instep (b) so as to form said dried mixture.
 30. A method in accordancewith claim 16 wherein said mixture and said incorporated mixture areeach dried in steps (b) and (e), respectively, at a temperature in therange of from about 65.5° C. to about 550° C.
 31. A method in accordancewith claim 16 wherein said dried incorporated mixture is calcined instep (e) at a temperature in the range of from about 204.4° C. to about815.5° C.
 32. A method in accordance with claim 16 wherein the reductionof said calcined incorporated mixture in step (g) is carried out at atemperature in the range of from about 37.4° C. to about 815.5° C. andat a pressure in the range of from about 15 to about 1500 psia and for atime sufficient to permit the formation of a reduced valence promoter.33. A method in accordance with claim 16 wherein during said calciningin step (e) at least a portion of said alumina is converted to analuminate.
 34. A method in accordance with claim 16 wherein said driedmixture from step (b) is calcined prior to said incorporating of step(c).
 35. A method in accordance with claim 34, wherein said driedmixture is calcined at a temperature in the range of from about 204.4°C. to about 815.5° C.
 36. A composition produced by the process of claim16.
 37. A process for the removal of sulfur from a hydrocarbon streamcomprising: (a) contacting said hydrocarbon stream with a compositionproduced by the process of claim 1 in a desulfurization zone underconditions such that there is formed a at least partially desulfurizedhydrocarbon stream and a sulfurized composition; (b) separating said atleast partially desulfurized hydrocarbon stream from said sulfurizedcomposition thereby forming a separated desulfurized hydrocarbon streamand a separated sulfurized composition; (c) regenerating at least aportion of said separated sulfurized composition in a regeneration zoneso as to remove at least a portion of the sulfur contained thereinand/or thereon thereby forming a regenerated composition; (d) reducingsaid regenerated composition in a reduction zone so as to provide areduced composition having a reduced valence promoter content thereinwhich will effect the removal of sulfur from sulfur-containinghydrocarbons when contacted with same; and thereafter (e) returning atleast a portion of said reduced composition to said desulfurizationzone.
 38. A process in accordance with claim 37 wherein said hydrocarbonstream comprises a fuel selected from the group consisting ofcracked-gasoline, diesel fuel, and combinations thereof.
 39. A processin accordance with claim 37 wherein said desulfurization in step (a) iscarried out at a temperature in the range of from about 37.8° C. toabout 537.8° C. and a pressure in the range of from about 15 to about1500 psia for a time sufficient to effect the removal of sulfur fromsaid stream.
 40. A process in accordance with claim 37 wherein saidregeneration in step (c) is carried out at a temperature in the range offrom about 37.8° C. to about 815.5° C. and a pressure in the range offrom about 10 to about 1500 psia for a time sufficient to effect theremoval of at least a portion of the sulfur from said separatedsulfurized composition.
 41. A process in accordance with claim 37wherein air is employed in step (c) as a regeneration agent in saidregeneration zone.
 42. A process in accordance with claim 37 whereinsaid regenerated composition from step (c) is subjected to reductionwith hydrogen in step (d) in said reduction zone which is maintained ata temperature in the range of from about 37.8° C. to about 815.5° C. andat a pressure in the range of from about 15 to about 1500 psia and for aperiod of time sufficient to effect a reduction of the valence of thepromoter content of said regenerated composition.
 43. A process inaccordance with claim 37 wherein said separated sulfurized compositionfrom step (b) is stripped prior to introduction into said regenerationzone in step (c).
 44. A process in accordance with claim 37 wherein saidregenerated composition from step (c) is stripped prior to introductionto said reduction zone in step (d).
 45. The cracked-gasoline product ofthe process of claim
 38. 46. The diesel fuel product of the process ofclaim
 38. 47. A process for the removal of sulfur from a hydrocarbonstream comprising: (a) contacting said hydrocarbon stream with acomposition produced by the process of claim 16 in a desulfurizationzone under conditions such that there is formed a desulfurizedhydrocarbon stream and a sulfurized composition; (b) separating saiddesulfurized hydrocarbon stream from said sulfurized composition therebyforming a separated desulfurized hydrocarbon stream and a separatedsulfurized composition; (c) regenerating at least a portion of saidseparated sulfurized composition in a regeneration zone so as to removeat least a portion of the sulfur contained therein and/or thereonthereby forming a regenerated composition; (d) reducing said regeneratedcomposition in an activation zone so as to provide a reduced compositionhaving a reduced valence promoter content therein which will effect theremoval of sulfur from a hydrocarbon stream when contacted with same;and thereafter (e) returning at least a portion of said reducedcomposition to said desulfurization zone.
 48. A process in accordancewith claim 47 wherein said hydrocarbon stream comprises a fuel selectedfrom the group consisting of cracked-gasoline, diesel fuel, andcombinations thereof.
 49. A process in accordance with claim 47 whereinsaid desulfurization in step (a) is carried out at a temperature in therange of from about 37.8° C. to about 537.8° C. and a pressure in therange of from about 15 to about 1500 psia for a time sufficient toeffect the removal of sulfur from said stream.
 50. A process inaccordance with claim 47 wherein said regeneration in step (c) iscarried out at a temperature in the range of from about 37.8° C. toabout 815.5° C. and a pressure in the range of from about 10 to about1500 psia for a time sufficient to effect the removal of at least aportion of the sulfur from said separated sulfurized composition.
 51. Aprocess in accordance with claim 47 wherein air is employed in step (c)as a regeneration agent in said regeneration zone.
 52. A process inaccordance with claim 47 wherein said regenerated composition from step(c) is subjected to reduction with hydrogen in step (d) in saidreduction zone which is maintained at a temperature in the range of fromabout 37.8° C. to about 815.5° C. and at a pressure in the range of fromabout 15 to about 1500 psia and for a period of time sufficient toeffect a reduction of the valence of the promoter content of saidregenerated composition.
 53. A process in accordance with claim 47wherein said separated sulfurized composition from step (b) is strippedprior to introduction into said regeneration zone in step (c).
 54. Aprocess in accordance with claim 47 wherein said regenerated compositionfrom step (c) is stripped prior to introduction to said reduction zonein step (d).
 55. The cracked-gasoline product of the process of claim48.
 56. The diesel fuel product of the process of claim 48.